Dehydrogenation catalyst

ABSTRACT

Magnesium chromites promoted with aluminum have been found to be superior to chromia-alumina type dehydrogenation catalysts, for example, in the dehydrogenation of n-butane. The aluminum is either added to the preformed magnesium chromite or is incorporated into the spinel structure of the chromite itself or added in both ways. The aluminum will be present in the catalyst from all sources in an atomic ratio of Al:Cr of 0.0004 to 1.2:1. The atomic ratio will more usually be 0.04 to 0.8:1, Al:Cr.

This is a division of application Ser. No. 475,608 filed June 3, 1974, now U.S. Pat. No. 3,960,975.

This invention relates to a process for the dehydrogenation of gaseous hydrocarbons and the catalyst employed. More specifically the process is a cyclic process wherein there are alternating cycles of dehydrogenation and catalyst regeneration.

The process is a cyclic process in which gaseous hydrocarbons such as butane or isopentane are dehydrogenated over a suitable catalyst to produce butenes and butadiene and isopentene and isoprene respectively. After each dehydrogenation cycle there is a catalyst regeneration cycle in which the accumulated coke is burned off by passing molecular oxygen through the catalyst followed by another dehydrogenation cycle and so on.

The chromia-alumina catalysts have been recognized for a number of years as the most preferred catalyst for this type of process. The chromia-alumina catalysts are prepared by treating activated alumina with a solution of chromic acid, draining off the excess acid from the alumina, drying and heat treating at about 1400° F. Commercial chromia-alumina dehydrogenation catalysts normally contain about 20% chromium oxide. Preparative methods are shown, for example, in U.S. Pat. Nos. 2,399,678 and 2,419,997.

Other chromia-metal oxide materials have been investigated for their dehydrogenation capabilities. One of the more prominent among these has been chromia-magnesia which has been found to be a poor second to chromia-alumina. Several U.S. patents were issued to Tropsch in the late 1930's relating to magnesia based chromia dehydrogenation catalysts, e.g., Nos. 2,122,786; 2,122,787; 2,122,790; and 2,148,140. Pitzer disclosed chromia-magnesia-alumina dehydrogenation catalyst in U.S. Pat. No. 2,638,455.

It is an object of the present invention to find an alternative catalyst to chromia-alumina for use in cyclic dehydrogenation processes. It is another object of the present invention to find a catalyst superior to the chromia-alumina catalysts for use in dehydrogenation. It is still a further object to provide a process which will give better results than presently achieved with chromia-alumina catalysts. Other objects and advantages of the present invention will be apparent from the following description.

DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

The objects of the present invention have been achieved by use of a novel catalyst containing chromium, magnesium, aluminum and oxygen. The catalysts are characterized as magnesium chromites either in admixture with aluminum oxide or containing aluminum therein and can be considered as aluminum promoted magnesium chromites. The chromites generally have a spinel structure. This can be attributed to the octahedral site preference energy of Cr³⁺ which is the greatest of all cations which can form spinel-type structures. The crystal structure of the chromites will usually be a face centered cubic form.

The catalysts of the present invention are predominately chromites, that is, they contain more than 50% by weight of the chromite. Preferably the catalysts contain 75% or more chromites, i.e., 90% chromites. The chromites generally may be represented by the formula MeCr₂ O₄ where Me as stated above is Mg, however, a portion of the magnesium can be replaced with other metals having an ionic radius approximately between about 0.5 and 1.1 A, preferably between about 0.6 and 1.0 A. In the case of such mixed chromites, Mg will be the predominant Me ion, comprising at least 50 atomic % of the Me ions present. In addition to Mg the Me may be one or more of the divalent ions of Ca, Sr, Ba, Fe, Mn, Co, Ni, Cu, Zn, or Cd.

The aluminum component of the catalyst may also be present as a constituent of the chromite, however, it is not necessary that the aluminum be a portion of the chromite and may be present in addition to the metal chromite in the form of aluminum oxide. The aluminum can be incorporated into the chromite by backing out a portion of the chromium. Aluminum can be substituted for up to less than 50% of the chromium atoms of the chromite. Such chromites have the formula MeAl_(x) CR_(2-x) O₄ where Me has the designation previously given and x is a number of from more than 0 up to less than 1.

The dehydrogenation catalyst comprises predominately magnesium chromite and a promoting amount of aluminium ion wherein the aluminum is present in the catalyst in an atomic ratio of Al:Cr of 0.0004 to 1.2:1 in (a) a compound of the formula MeAl_(x) Cr_(2-x) O₄, where Me is Mg or Mg and one or more of the divalent ions of Ca, Sr, Ba, Fe, Mn, Co, Ni, Cu, Zn or Cd, provided that Mg comprises at least 50 atomic percent of said Me ions and x is a number of from more than 0 up to less than 0, (b) aluminum oxide or (c) a combination of (a) and (b).

The magnesium chromites of the present invention exhibit a certain type of X-ray diffraction pattern. The peaks observed in the X-ray diffraction pattern may not have sharp peaks such as those found, e.g., in highly crystalline material of the same chemical composition, but can and do frequently exhibit relatively broad reflection peaks. The degree of sharpness of the reflection peak may be measured by the reflection peak band width at half height (W/h/2). In other words, the width of the reflection peak as measured at one-half of the distance to the top of the peak is the "band width at half height". The band width at half height is measured in units of °2 theta. Techniques for measuring the band widths are discussed, e.g., in Chapter 9 of Klug and Alexander, X-ray Diffraction Procedures, John Wiley and Son, N.Y., 1954. The observed band widths at half height of the preferred compositions of this invention are at least 0.12°2 theta and normally will be at least 0.16°2 theta.* The particular reflection peak used to measure the band width at one-half height is the reflection peak having Miller (hkl) indices of 111. (See, e.g., Chapter of Klug and Alexander, ibid). This description is not to be taken as a limitation of the invention in regard to the relationship between composition activity and band width.

Suitable catalyst according to this invention are magnesium chromite having X-ray diffraction peaks within the d-spacings 480-482, 294-296, 250-252, 240-242, 207-209, 190-192, 169-171, 159-161, 146-148, 140-142, and the most intense peaks being between 250-252.

Chromite formation can be accomplished by reacting an active compound of chromium with an active compound of magnesium and the other designated metals. By active compound is meant a compound which is reactive under the conditions to form the chromite. Starting compounds of chromium, magnesium or the other metals may be such as the nitrates, hydroxides, hydrates, oxalates, carbonates, acetates, formates, halides, oxides, etc.

The catalyst may contain an excess of chromium over the stoichiometric amount, which is 2 atoms of chromium per atom of Me (MeCr₂ O₄). There may be from 10 to 200 percent excess of the chromium. Similarly the Me portion of the chromite may be present in more than a stoichiometric amount.

The magnesium chromite can be prepared by precipitation, dry or wet milling or mixing, by precipitation of one of the ingredients in the presence of the other, coprecipitation and impregnation of one or more of the solid ingredients with aqueous or non-aqueous solutions of salts of the ingredients.

One particularly useful method of preparing the magnesium chromites has been by coprecipitation from an aqueous solution. Soluble metal salts of chromium, magnesium and any other metal component as described above are dissolved in water and an insoluble precipitate formed by the use of a precipitating agent.

Soluble metal salts are known for essentially all metals. In specific regard to the metal components of the present invention the following soluble metal compounds are illustrative: chromium (III) nitrate, magnesium chloride, calcium sulfate, strontum tetrasulfide tetrahydrate, barium trisulfide, iron (II) nitrate, manganese (II) dithionate, cobalt (II) acetate, nickel nitrate, copper nitrate, zinc sulfate, cadimum sulfate and aluminum sulfate. The precipitating agent in any compound which when reacted with the metal ion portion of the catalyst forms an insoluble compound which can be converted to the chromite. The alkali and alkaline earth hydroxides such as NaOH, KOH, CaOH, as well as ammonium hydroxide cause the precipitation of the metal hydroxides which are converted on heating to the chromites. After the precipitate is washed and dried it is calcined to form the chromite.

The formation of the chromite is obtained by heating the precipitates or other intimate mixture of chromite precursors at an elevated temperature, e.g., 400°-1100° C. (generally no greater than 1300° C.), in a controlled atmosphere, i.e., air nitrogen, helium, a reducing atmosphere such as hydrogen, carbon monoxide or the like, for a sufficient time, i.e., usually 5 minutes to 4 hours. A calcination temperature of 550°-800° C. has been found particularly useful and temperatures in the range of 600°-750° C. have been found to produce excellent catalysts. Catalysts prepared at 900°-1100° C. have also been found to be highly desirable.

The aluminum component of the catalyst as stated above can be added prior to and/or after the calcination and formation of the chromite. The aluminum component is conveniently added to the chromite as a soluble salt in a slurry with the chromite after which it is dried then decomposed by heating to aluminum oxide. Alternatively insoluble aluminum oxide can be added to the magnesium chromite, preferably in a highly divided state. Yet another desirable way to place the aluminum in the catalyst is by coprecipitation of aluminum hydroxide with the Me hydroxide and chromium hydroxide.

The aluminum will be present in the catalyst in all forms in an atomic ratio of Al:Cr of 0.0004 to 1.2:1. For example, in terms of a soluble aluminum compound such as aluminum sulfate, added to the magnesium chromite this would represent from about 0.1 to 75 weight percent Al₂ (SO₄)₃ 16H₂ O based on the total weight of the catalyst. A more preferred range of Al:Cr atom ratio is 0.04 to 0.8:1. Generally the higher weight percentages of aluminum compound, i.e., 50 weight percent or more, are applied to the magnesium chromites having high surface areas, e.g., 50m² per gram or more.

The active catalysts can be pelleted or applied to a suitable support, such as alumina, silica gel, silica-alumina, firebrick, kieselguhr, quartz and the like. The catalyst is the active surface available for contact with the gaseous reactants.

The catalysts of this invention can be applied to the dehydrogenation of a wide variety of organic compounds. Such compounds normally will contain from 2 to 20 carbon atoms, at least one ##STR1## having a boiling point below about 350° C., and may contain other elements, in addition to carbon and hydrogen such as oxygen, halogens, nitrogen and sulfur. Preferred are compounds having 2 to 12 carbon atoms, and especially preferred are compounds of 3 to 5 carbon atoms.

Representative materials which are dehydrogenated by the novel process of this invention include n-butane, ethyl toluene, alkyl chlorobenzenes, ethyl naphthalene, isobutyronitrile, propyl chloride, isobutyl chloride, ethyl fluoride, ethyl bromide, n-pentyl iodide, ethyl dichloride, 1,3-dichlorobutane, 1,4 dichlorobutane, the chlorofluoroethanes, methyl pentane, methylethyl ketone, diethyl ketone, n-butyl alcohol, methyl propionate, and the like.

Among the types of organic compounds which may be dehydrogenated by means of the process of this invention are nitriles, amines, alkyl halides, ethers, esters, aldehydes, ketones, alcohols, acids, alkyl aromatic compounds, alkyl heterocyclic compounds, cycloalkanes, alkanes, alkenes and the like.

Suitable dehydrogenation reactions are the following: acyclic compounds having 4 to 5 non-quarternary contiguous carbon atoms to the corresponding olefins, diolefins or acetylenes having the same number of carbon atoms; aliphatic hydrocarbons having 6 to 16 carbon atoms and at least one quaternary carbon atom to aromatic compounds, such as 2,4,4-trimethylpentene-1 to a mixture of xylenes; acyclic compounds having 6 to 16 carbon atoms and no quaternary carbon atoms to aromatic compounds such as n-hexenes to benzene; cycloparaffins and cycloolefins having 5 to 8 carbon atoms to the corresponding olefin, diolefin or aromatic compound, e.g., cyclohexane to cyclohexene or cyclohexadiene or benzene; aromatic compounds having 8 to 12 carbon atoms including one or two alkyl side chains of 2 to 3 carbon atoms to the corresponding aromatic with unsaturated side chain such as ethyl benzene to styrene.

Illustration of dehydrogenations include butane to butenes and butadiene propionitrile to acrylonitrile; propionaldehyde to acrolein; ethyl chloride to vinyl chloride; methyl isobutyrate to methyl methacrylate; 2 or 3-chlorobutene-1 or 2,3-dichlorobutane to chloroprene; ethyl pyridine to vinyl pyridine; ethylbenzene to styrene; isopropylbenzene to α-methyl styrene; ethylchlorohexane to styrene; cyclohexane to benzene; ethane to ethylene to acetylene; propane to propylene or methyl acetylene, allene, or benzene; isobutane to isobutylene; n-butane to butene and butadiene-1,3; n-butene to butadiene-1,3 and vinyl acetylene; methyl butene to isoprene; cyclopentane to cyclopentane and cyclopentadiene-1,3; n-octane to ethyl benzene and ortho-xylene; monomethylheptanes to xylenes; ethyl acetate to vinyl acetate; 2,4,4-trimethylpentane to xylenes; and the like.

The preferred compounds to be dehydrogenated are hydrocarbons with a particularly preferred class being acyclic non-quaternary hydrocarbons having 3 to 5 carbon atoms or ethyl benzene and the preferred products are propene, n-butene-1 or 2, butadiene-1,3, vinyl acetylene,2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-2-butene, isoprene, styrene or mixtures thereof. Especially preferred as feed are n-butene-1 or 2 and the methyl butenes and mixtures thereof such as hydrocarbon mixtures containing these compounds in at least 50 mol percent.

The dehydrogenation reaction may be carried out at atmospheric pressure, superatmospheric pressure or at sub-atmospheric pressure. The total pressure of the system will normally be about atmospheric pressure or sub-atmospheric pressure. Generally the total pressure will be between about 1 p.s.i.a. and about 75 p.s.i.a. Preferably the total pressure will be less than about 50 p.s.i.a.

The temperature of the dehydrogenation reaction will generally be in a range of about 350° to 700° C. with excellent results being obtained in the range of 400° to 650° C. The gaseous reactants can be conducted through the reaction chamber at a fairly wide range of flow rates. The optimum flow rates will be dependent upon such variables as the temperature of reaction, pressure, particle size of the catalyst, and so forth. Desirable flow rates may be established by one skilled in the art. Generally the flow rates will be within the range of about 0.10 to 10 liquid volumes of the organic compound to be dehydrogenated per volume of dehydrogenation zone containing catalyst per hour (referred to as LHSV). Usually the LHSV will be between 0.15 and about 5. For calculation, the volume of a fixed bed dehydrogenation zone containing catalyst is that original void volume of reactor space containing catalyst.

The dehydrogenation is carried out in a series of cycles which comprise dehydrogenation of a suitable feed over the catalysts of the invention under the conditions as defined for a period of time, usually about 6 to 12 minutes followed by a regeneration cycle during which the coke deposited from the dehydrogenation is burnt off. The regeneration can no longer be shorter than the dehydrogenation cycle as needed to remove the coke, usually about 6 to 12 minutes will be sufficient. The coke is removed by passing oxygen at a temperature of 550° to 650° C. over the catalyst. A convenient source of oxygen is air, however, pure oxygen or a mixture of oxygen with inert gases, such as nitrogen, either in the same or different proportions as air, can be used.

The following Examples which are submitted to demonstrate the operation of the invention are divided into two sections relative to the reactor. In the first Example section the process was carried out at atmospheric pressure, i.e., about 15 p.s.i.a. In the second section the reactions were carried out under vacuum. The absolute number of the results vary as a result of the different conditions, however, the trends, results and relative differences in catalysts types are comparable. The presence of the chromite structure was established for the catalysts by X-ray analysis as described previously. In the Examples percents are by weight except that results are given as mole percents. Analysis of the products was by gas-liquid chromatography.

EXAMPLE 1

The coprecipitated catalysts were prepared by the same method. In each instance CrCl₃.6H₂ O and MgCr₂.6H₂ O (in some cases AlCl₃.6H₂ O) were dissolved in demineralized water with about 1.4% dextran* to produce an atom ratio of Mg/Cl of 1/2 unless specified otherwise. This solution was then added to concentrated NH₄ OH, the precipitate filtered, washed and dried at 160° C. then passed through an 80 mesh screen and calcined for 1 hour at the indicated temperature in air (unless specified otherwise) and ran through a hammer mill. The soluble salts, e.g., Al₂ (SO₄)₃.16H₂₀, were added by dissolving the salt in water, forming a slurry with the chromite (or in some cases the comparative commercial catalyst) and heating the slurry to dryness in a mechanical tumbler to obtain even distribution of the soluble salts. The same procedure was used to deposit the actives on a support.

ISOTHERMAL ATMOSPHERIC REACTOR (EXAMPLES 2-23)

The reactor was a 29×3/4 inch Vycer tube equipped with a heating mantle and appropriate equipment. A 40 cc bed of catalyst was placed in the reactor and reactant feed (or regenerative air) added at the bottom of the reactor with product coming off overhead. The catalyst was heated to the reaction temperature in a nitrogen atmosphere. The process was carried out automatically with a make cycle (dehydrogenation) of 9 minutes and 9 minutes oxygen regeneration and repeat of the cycle. This gave a total cycle time of 18 minutes. When desired, the partial pressure of the n-butane during the reaction cycle was reduced below atmospheric by dilution with nitrogen. The total effluent from either or both cycles was collected in an inflatable collecting device and analyzed by gas chromatography. Alternatively, the effluent from the regeneration cycle was passed through a calibrated infrared analyzer to determine the amount of CO₂ produced during regeneration (coke burn-off). By either method of analysis the amount of coke deposited on a catalyst during the reaction cycle was determined and could be taken into account when calculating the overall activity and selectivity of a catalyst. The temperatures were controlled by a thermoelectric temperature controller and recorded on a Leeds and Northrup 24-point recorder.

EXAMPLES 2-11

These Examples demonstrate the improvement accomplished according to the present invention. The feed was 99 mole % n-butane. The conditions and results are set out in Table 1.

                                      TABLE 1                                      __________________________________________________________________________     Conditions: LHSV = 1.0 T.sub.m = ˜ 600° C. Reaction Cycle =       9 minutes reaction/                                                            9 minutes regeneration                                                                            Partial                                                     Ex-                Pressure                                                                             Total  Results Mole %                                 am-                n-C.sub.4                                                                            Hrs. on                                                                               S    Y                                         ple                                                                               Catalyst        (Atm.).sup.3                                                                         Stream                                                                              C Bu                                                                               Bd Bu Bd                                     __________________________________________________________________________     2  Marshaw.sup.7 Cr0211,5/32"                                                                     1.0   24   69                                                                               65                                                                               5  45 4                                         diameter pellets                                                                               0.33  26   67                                                                               69                                                                               10 46 7                                      3  Houdry.sup.8 C, 1/8"                                                                           1.0   24   77                                                                               64                                                                               8  49 7                                         extrusions      0.33  26   79                                                                               65                                                                               10 50.5                                                                              13                                     4  5/32" pellets of                                                                               1.0   24   44                                                                               54                                                                               8.5                                                                               24 4                                         MgCr.sub.2 O.sub.4                                                                             0.33  26   38                                                                               48                                                                               16 18 6                                      5  5/32" pellets of                                                                               1.0   24   57                                                                               67                                                                               9  38 5                                         MgCr.sub.2 O.sub.4 + 26 wt. %                                                                  0.33  26   56                                                                               66                                                                               15 37 8                                         Al.sub.2 (SO).sub.4).sub.3 . 18H.sub.2 O                                    6  5/32" pellets MgCr.sub.2 O.sub.4                                                               1.0   24   58                                                                               66                                                                               8  38 5                                         .sup.6 + 20% Al.sub.2 (SO.sub.4).sub.3 .                                                       0.33  26   55                                                                               63                                                                               15 35 8                                         18H.sub.2 O                                                                 7  MgCr.sub.2 O.sub.4,.sup.1,2,4                                                                  1.0   24   51                                                                               64                                                                               8  33 4                                                         0.33  26   46                                                                               61                                                                               15 28 7                                      8  MgCr.sub.2 O.sub.4.sup.1,2,4 +                                                                 1.0   24   59                                                                               66                                                                               8  39 5                                         0.012 mols      0.33  26   57                                                                               63                                                                               14 36 8                                         Al.sub.2 (SO.sub.4).sub.3.18H.sub.2 O                                       9  MgCr.sub.2 O.sub.4.sup.1,2,4 + 0.024                                                           1.0   24   64                                                                               69                                                                               8  47 5                                         Moles Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                                  0.33  26   66                                                                               68                                                                               14 44 9                                      10 MgCr.sub.2 O.sub.4.sup.1,2,4 +                                                                 1.0   24   66                                                                               68                                                                               8  45 5                                         0.037 moles     0.33  26   68                                                                               67                                                                               15 46 10                                        Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                     11 MgCr.sub.2 O.sub.4.sup.1,2,4 + 0.012                                                           1.0   24   52                                                                               62                                                                               8  32 4                                         mols H.sub.2 SO.sub.4                                                       __________________________________________________________________________      Notes:                                                                         .sup.1 Coprecipitate of Cr/Mg 2/1 calcined at 600° C. for 1 hour i      air                                                                            .sup.2 Catalyst are 6-8 mesh particles of ˜55% actives deposited on      7-9 mesh, HCl leached AMC alumina                                              .sup. 3 pp of n-C.sub.4 = 1.0 atm. = pure heba feed; pp of n-C.sub.4 =         0.33 atm. = hcbn + N.sub.2 diluent                                             .sup.4 66.7 gms. of MgCr.sub.2 O.sub.4                                         .sup.5 C = conversion, S = selectivity, Y = yield, Bu = butenes, Bd =          betadiene.                                                                     .sup.6 Uncalcined coprecipitate Cr/Mg =2/1 + 20% Al.sub.2 (SO.sub.4).sub.      . 18H.sub.2 O then calcined at 600° C. for 2 hours in air               .sup.7 The Marshaw Chemical Co., Cleveland Ohio                                .sup.8 Houdry Products and Chemical Co., Philadelphia, Pa.               

Examples 1 and 2 are two commercial catalyst employed in cyclic processes for dehydrogenation of butane. Examples 4 and 5 are MgCrO₄ which was pelleted and 6 through 10 are 55% actives deposited on a fused alumina support. Example 11 was to determine if the sulfate was of any benefit. By comparison of Examples 11 and 7 it can be seen that the sulfate is of no benefit.

EXAMPLES 12 and 13

These Examples show the improvement obtained with aluminum salts other than the sulfate using 99 mole % butane as the feed. The conditions and results are set out in TABLE II.

                  TABLE II                                                         ______________________________________                                         Conditions: LHSV = 1.0 T.sub.m =0 ˜600° C.,                       Reaction Cycle = 9 minutes reaction/                                           9 minutes regeneration                                                                               Partial                                                  Ex-                   Pressure     Results Mole %                              am-                   of n-C.sub.4 S     Y                                     ple  Catalyst.sup.1   (Atm.).sup.2                                                                            C   Bu  Bd  Bu  Bd                              ______________________________________                                         12   42.5 gms. MgCr.sub.2 O.sub.4.sup. =                                                             1.0      58  67   9  39  5                                    0.044 moles of   0.33     52  61  17  32  9                                    Al(CH.sub.3 COCHCOCH.sub.3).sub.3                                         13   42.5 gms. of MgCr.sub.2 O.sub.4.sup.3                                                           1.0      62  70   8  43  5                                    + 0.044 moles of 0.33     61  68  15  41  9                                    Al(NO.sub.3).sub.3 . 9H.sub.2 O                                           ______________________________________                                          .sup.1 Supported on 7-9 mesh AMC alumina                                       .sup.2 pp of n-C.sub.4 = 1.0 atm. = pure hebn feed: pp of n-C.sub.4 = 0.3      atm. =  hcbn + N.sub.2                                                         .sup.3 coprecipitated, calcined at 600° C. for 2 hours in air and       run through a hammer mill.                                               

EXAMPLES 14-19

These Examples demonstrate the effect of the calcination temperature of the MgCr₂ O₄ on the process results. Table III shows the conditions and results.

                                      TABLE III                                    __________________________________________________________________________     Conditions: LHSV = 1.0 T.sub.m = ˜600° C.                         Reaction Cycle = 9 minutes reaction/                                           9 minutes regeneration approx. 24 hours on stream for each run                 Feed n-butane (99 mole %)                                                                       Partial                                                       Ex-              Pressure                                                                            Results                                                  am-              of n-C.sub.4                                                                           S     Y                                               ple                                                                               Catalyst.sup.(1)                                                                             (Atm.).sup.(2)                                                                      C  Bu Bd Bu                                                                               Bd                                            __________________________________________________________________________     14 Coprec. of Cr/Mg =                                                                           1.0  67 68 10 45                                                                               7                                                2/1 calcined to 550° C.;                                                              0.33 66 65 17 43                                                                               11                                               42.5 gms. of calcined                                                          product + 0.022 moles                                                          of Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                  15 Coprec. pf Cr/Mg =                                                                           1.0  67 68 10 45                                                                               7                                                2/1 calcined to 600° C.;                                                              0.33 68 65 18 43                                                                               12                                               42.5 gms. of calcined                                                          product + 0.022 moles of                                                       Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                     16 Coprec. of Cr/Mg =                                                                           1.0  68 70 9  48                                                                               6                                                2/1 calcined to 650° C.;                                                              0.33 67.5                                                                              70 15 47                                                                               10                                               42.5 gms of calcined                                                           product + 0.022 moles                                                          of Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                  17 Coprec. of Cr/Mg =                                                                           1.0  59 76 10 45                                                                               6                                                2/1 calcined to 700° C.;                                                              0.33 55 74 17.5                                                                              41                                                                               10                                               42.5 gms of calcined                                                           product + 0.022 moles                                                          of Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                  18 Coprec. of Cr/Mg = 2/1                                                                       1.0  60 74 9  45                                                                               5                                                calcined to 750° C., 42.5                                                             0.33 58 76 16 44                                                                               9                                                gms. of calcined product                                                       + 0.022 moles of                                                               Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                     19 Coprec. of Cr/Mg = 2/1                                                                       1.0  47 77 11 37                                                                               5                                                calcined to 800° C.;                                                                  0.33 42 72.5                                                                              20 31                                                                               8                                                42.5 gms. of calcined                                                          product + 0.022 moles                                                          of Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                  __________________________________________________________________________      Notes:                                                                         .sup.(1) Supported on 7-9 mesh AMC alumina                                     .sup.(2) pp of n-C.sub.4 = 1.0 atm. = pure hcbn feed; pp of n-C.sub.4 =        0.33 atm. = hcbn + N.sub.2.                                              

The noticeable trends with increasing calcination temperature are the decrease in conversion but substantial increase in selectivities.

EXAMPLES 20 and 21

These examples are presented to show the combination of Al in a chromite of the formula MgAl_(x) Cr_(2-x) O₄. Table IV sets forth the concition and results.

                  TABLE IV                                                         ______________________________________                                         Conditions: LHSV = 1.0, T.sub.m = 600° C.;                              Reaction Cycle = 9 minutes reaction/                                           9 minutes regeneration.                                                        Feed : 99 moles % butane                                                       Hours on stream ≃ 24                                                                Partial                                                     Ex-                Pressure Results                                            am-  x in          n-C.sub.4    S      Y                                       ple  MgAl.sub.x Cr.sub.2-x O.sub.4.sup.(1)                                                        (Atm.).sup.(2)                                                                          C   Bu  Bd   Bu   Bd                               ______________________________________                                         20   0.0           1.0      51  74  7    37.5 3                                     0.1           1.0      63  67  8    42   5                                     0.2           1.0      64  65  9    42   6                                     0.3           1.0      66  68  7    45   5                                     0.4           1.0      67  69  6.5  47   4                                     0.5           1.0      68  69  8    47   5.5                              21   0.0           0.33     42  64  15   27   6                                     0.1           0.33     62  65  15   40   9                                     0.2           0.33     62  64  16   40   10                                    0.3           0.33     69  69  12   48   8.5                                   0.4           0.33     67  66  14   44   9                                ______________________________________                                          Notes:                                                                         .sup.1 6-8 mesh particles of 50 wt. % actives deposited on 7-9 mesh, HCl       leached AMC alumina support.                                                   .sup.(2) pp of n-C.sub.4 = 1.0 atm. = pure hcbn feed; pp of n-C.sub.4 =        0.33 atm. = hcbn + N.sub.2 diluent.                                      

The catalysts were prepared in the same manner as in Example I with Al₂ (SO₄)₃ being added in the appropriate amount. The coprecipitated catalysts were calcined at 600° C. for 2 hours in air and hammer milled.

No substantial advantage was obtained from adding an additional 20% Al₂ (SO₄)₃ 18H₂ O to the calcined MgAl_(x) Cr_(2-x) O₄ catalyst.

EXAMPLE 22

The catalyst in this case was prepared by depositing a slurry of 4.4% Al₂ O₃ and 95.6% MgCr₂ O₄ (calcined coprecipitated at 600° C. for 2 hours in air) on to HCl leached alumina and drying the catalyst. 4.4% Al₂ O₃ corresponds to 20% Al₂ (SO₄)₃.16H₂ O. The Al₂ O₃ was approximately 90% gamma alumina (Alon fumed alumina). The dehydrogenation was carried out at 1 atmosphere using pure n-butane at LHSV of 1 at 600° C. for about 24 hours using the 9/9 minute cycle. The results were

    ______________________________________                                         Mole %                                                                         C       S.sub.Bu  S.sub.Bd  Y.sub.Bu                                                                               Y.sub.Bd                                   ______________________________________                                         60      74        12        44      7                                          ______________________________________                                    

EXAMPLE 23

This series of runs was made to demonstrate the catalyst with an excess of either Mg or Cr over the stoichiometric amount. The variation was obtained by using the proportion of soluble salts to give the Mg:Cr atom ratio shown in Table V. The improvement for each ratio with added Al is also shown in Table V along with the conditions.

                                      TABLE V                                      __________________________________________________________________________     Conditions: LHSV = 1.0, atmospheric pressure temperature ≃       600° C.,                                                                reaction cycle 9 minutes reaction/9 minutes regeneration.                      Feed: 99 mole % n-butane                                                                   Results                                                                        Without Al 20%:Al.sub.2 (SO.sub.4).sub.3. 16H.sub.2 O                          Mole %     Mole %                                                              S     Y      S     Y                                               x in Mg.sub.1.0 Cr.sub.x O.sub.4                                                        C  Bu   Bd                                                                              Bu   Bd                                                                             C Bu   Bd                                                                              Bu   Bd                                         __________________________________________________________________________     1.7      36 65 + 12                                                                              24 + 4                                                                              62                                                                               68 + 13                                                                              42 + 8                                          1.8      44 69 + 10                                                                              30 + 5                                                                              67                                                                               63 + 15                                                                              42 + 10                                         1.9      42 68 +11                                                                               29 + 5                                                                              67                                                                               65 +11                                                                               44 + 8                                          2.0      46 67 +10.5                                                                             31 + 5                                                                              64                                                                               65 +12                                                                               42 + 8                                          2.1      41.5                                                                              64 +12                                                                               27 + 5                                                                              69                                                                               68 +12                                                                               47 + 8                                          2.2      42 61 +12                                                                               26 + 5                                                                              65                                                                               66 +11                                                                               43 + 7.5                                        2.3      41 57 +13                                                                               24 + 5                                                                              64                                                                               58 +12.5                                                                             44 + 8                                          __________________________________________________________________________

ISOTHERMAL VACUUM REACTOR (EXAMPLES 24-47)

The reactor was an alonized 316 SS tube, 24 inches long and 1 inch in diameter equipped with a heating mantel and thermoelectric temperature controller. A 160 cc bed of catalyst (112 cc of catalyst mixed with 48 cc of fused alumina balls) was used for each run. The reactant feed was passed down through the catalyst bed and the products removed at the bottom. The catalyst was heated to reaction temperature in a nitrogen atmosphere. The process was carried out in cycles of 9 minutes of reaction, 1 minute of nitrogen purge, 9 minutes of regeneration, followed by reaction, etc. A vacuum of 22 inches of Hg was maintained during the reaction cycle and atmospheric pressure used during nitrogen purge and regeneration cycle. Substantially the same analytical procedures were followed for the product gases as in the atmospheric process.

EXAMPLES 24-27

These four examples demonstrate the invention having the aluminum compound added after (Ex. 25) and before (Ex. 26) calcination. Example 24 is the control. Table VI contains the conditions and results of the run.

                                      Table VI                                     __________________________________________________________________________     Conditions: LHSV = 1.25, I.sub.m = ˜ 550° C. (1022°        F.), Pressure =  22" Hg vacuum                                                                          9 min. regeneration                                   9 min. reaction          1500 cc/min. of artificial                            Reaction Cycle = 590 cc/min.                                                                  1 min. N, air = 300 cc/min. O.sub.2 +                             of n-C.sub.4 purge     1200 cc/min. N.sub.2,                                 Feed: 99 mole % n-butane                                                       Ex-                      Results, Mole %                                       am-               Total Hrs.                                                                              S     Y                                             ple Catalyst      on Stream                                                                             C Bu   Bd  Bu  Bd                                     __________________________________________________________________________     24  5/32" dia. MgCr.sub.2 O.sub.4                                                                90.5   22.4/70.8 + 10.6/15.8 + 2.4                               (coprec. of Cr/Mg =                                                                          138.5  21.1/68.4 + 11.2/14.4 + 2.4                               2/1 calcined to 600° C.                                                               206.0  19.8/67.1 + 12.0/13.3 + 2.4                           25  5/32" dia. pellets of                                                                        21.5   50.2/77.0 + 6.9/38.6 + 3.5                                MgCr.sub.2 O.sub.4 (copree. of                                                               44.5   61.0/72.1 + 7.9/44.0 + 4.8                                Cr/Mg = 2 1 calcined                                                                         120.5  60.2/73.6 + 8.0/44.3 + 4.8                                to 600° C. + 20 wt. %                                                                 334.5  59.7/73.7 + 6.0/44.0 + 3.6                                Al.sub.2 (SO.sub.4).sub.3 + 18H.sub.2 O.sup.(2)                                              501.5  58.5/76.7 + 5.8/44.8 + 3.4                            26  non-calcined coprec.                                                                         115.0  44.5/74.3 + 10.5/33.1 + 4.7                               of Cr/Mg = 2/1 +                                                                             161.0  44.9/76.0 + 10.3/34.1 + 4.6                               appropriate amount of                                                                        234.0  40.4/76.5 + 10.1/30.9 + 4.1                               Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O and                                                  334.0  39.3/77.6 + 11.1/30.5 + 4.4                               the mixture calcined to                                                        600° C. and formed into                                                 5/32" dia. MgCr.sub.2 O.sub.4                                                  pellets                                                                    27  5/32" dia. pellets                                                                           95.0.sup.(1)                                                                          67.8/63.7 + 7.1/43.2 + 4.8                                MgCr.sub.2 O.sub.4 coprec. of                                                                190.5.sup.(1)                                                                         64.5/66.6 + 8.4/42.9 + 5.4                                Cr/Mg = 2/1 calcined                                                                         214.5.sup.(2)                                                                         53.5/75.1 + 7.1/40.2 + 3.8                                to 600° C. + 38 wt. %                                                                 239.0.sup.(2)                                                                         55.4/75.6 + 7.2/41.9 + 4.0                                Al(NO.sub.3).sub.3 + 9H.sub.2 O                                                              334.0.sup.(2)                                                                         56.3/75.1 + 7.1/42.3 + 4.0                                              382.5.sup.(2)                                                                         57.1/74.6 + 7.4/42.6 + 4.2                                              526.5.sup.(2)                                                                         55.1/77.2 + 8.4/42.9 + 4.7                            __________________________________________________________________________      .sup.(1) Flow of O.sub.2 was increased from 300 cc/min to 345 cc/min to        effect complete regeneration.                                                  .sup.(2) T.sub.m = 525° C.                                        

EXAMPLES 28, 29 AND 30

These examples show a range of aluminum concentrations in the catalyst. Table VII shows the conditions and results.

                                      TABLE VII                                    __________________________________________________________________________     Conditions: LHSV = 1.25      Pressure =  22" Hg vacuum                                                      9 min. regeneration.                              9 min. reaction              1500 cc/min. of artificial                        Reacton Cycle = 590 cc/min                                                                       1 min.N.sub.2                                                                             air = 300 cc/min. O.sub.2 +                       of n-C.sub.4.     purge      1200 cc/min. N.sub.2.                             Feed: 99 mole % n-butane                                                       Ex-                          Results, Mole %                                   am                Total Hrs.                                                                             T.sub.m,                                                                          S     Y                                           ple Catalyst      on Stream                                                                             ° C.                                                                        C Bu   Bd   Bu   Bd                               __________________________________________________________________________     28  5/32" dia. pellets of                                                                        23.0   550 56.8/71.5 + 9.2/40.6 + 5.2                            MgCr.sub.2 O.sub.4 (coprec. of                                                               94.5   550 59.4/70.5 + 9.3/41.9 + 5.5                            Cr/Mg = 2/1 cal-                                                                             117.5  550 60.2/69.1 + 9.6/41.6 + 5.8                            cined to 700° C.)+15                                                                  141.5  550 60.0/70.3 + 9.8/42.2 + 5.9                            wt. % Al.sub.2 SO.sub.4).sub.3 . 16                                                          165.5  525 50.5/78.6 + 7.9/39.7 + 4.0                            H.sub.2 O     189.5  525 52.1/79.1 + 7.3/41.2 + 3.8                        29  5/32" dia. pellets of                                                                        69.5   550 56.0/72.2 + 9.0/40.5 + 5.1                            MgCr.sub.2 O.sub.4 (coprec. of                                                               97.5   550 57.7/73.1 + 8.6/42.2 + 4.9                            Cr/Mg = 2/1 cal-                                                                             117.5  550 59.2/75.1 + 8.8/44.5 + 5.2                            cined to 700° C.) +20                                                                 165.5  550 59.0/73.2 + 8.9/43.1 + 5.2                            wt. % Al.sub.2 (SO.sub.4).sub.3 .16                                                          238.0  550 59.4/73.0 + 9.8/43.4 + 5.8                            H.sub.2 O                                                                  30  5/32" dia. pellets of                                                                        67.0   550 59.3/71.2 + 11.0/42.2 + 6.5                           MgCr.sub.2 O.sub.4 (coprec. of                                                               90.5   550 59.7/71.1 + 10.9/42.4 + 6.5                           Cr/Mg = 2/1 cal-                                                                             186.0  550 60.1/71.8 + 10.3/43.1 + 6.2                           cined to 700° C.) +                                                                   321.0  525 48.2/81.5 + 7.8/39.3 + 3.7                            25 wt. % Al.sub.2 (SO.sub.4).sub.3 .                                           16H.sub.2 O                                                                __________________________________________________________________________

EXAMPLES 31-34

The effect of the calcination temperature is shown in these examples. As in the reaction run at atmospheric pressure the MgCr₂ O₄ produced at increasing calcination temperatures provided higher selectivities with lower conversions under similar operating conditions. This can be seen in Table VIII.

                                      TABLE VIII                                   __________________________________________________________________________     Conditions: LHSV = 1.25,                                                                      T.sub.max ˜ 550° C.,                                                         Pressure = 22" Hg vacuum                                                       9 min. regeneration                                  9 min. reaction           1500 cc/min. of artificial                           590 cc/min.               air = 300 cc/mn. O.sub.2 +                           of n-C.sub.4   1 min. N.sub.2 purge                                                                      1200 cc/min. N.sub.2                                 Feed: 99 mole % n-butane                                                       Ex-                       Results, Mole %                                      am-            Total Hrs.                                                                            T.sub.m                                                                              S     Y                                            ple Catalyst.sup.(1)                                                                          on Stream                                                                             ° C.                                                                        C Bu   Bd   Bu   Bd                                  __________________________________________________________________________     31  MgCr.sub.2 O.sub.4 calcined                                                               164.5  550 65.7/64.9 + 11.9/42.6 + 7.8                              to 600° C.                                                                         282.5  525 56.2/75.9 +  8.3/42.7 + 4.5                          32  MgCr.sub.2 O.sub.4 calcined                                                               164.0  550 65.3/69.1 + 11.1/45.1 + 7.3                              to 650° C.                                                                         235.0  525 53.4/75.3 +  9.4/40.2 + 5.0                          33  MgCr.sub.2 O.sub.4 calcined                                                               307.5  550 55.9/69.3 + 14.1/38.7 + 7.9                              to 700° C.                                                          34  MgCr.sub.2 O.sub.4 calcined                                                               503.0  570 56.2/68.3 + 17.6/38.4 + 9.9                              to 750° C.                                                                         743.5  550 51.2/76.7 + 13.5/39.3 + 6.9                          __________________________________________________________________________      Note:                                                                          .sup.(1) MgCr.sub.2 O.sub.4 + 25 wt. % Al.sub.2 (SO.sub.4).sub.3 .             16H.sub.2 O formed into 5/32" pellets.                                   

EXAMPLES 35-42

These examples are presented by way of comparison to show the total lack of effectiveness of aluminum on two commercial dehydrogenation catalysts of the chromia-alumina type. The data is presented in Table IX.

                                      TABLE IX                                     __________________________________________________________________________     Conditions: LHSV = 1.25,                                                                            T.sub.m = ˜ 550° C.(1022°                                           Pressure = 22" Hg vacuum,                                                      9 min. regeneration                              9 min. reaction               1500 cc/min. of artificial                       Reacton Cycle - 590 cc/min.   air = 300 cc/min. O.sub.2 +                      of n-C.sub.4         1 min. N.sub.2 purge                                                                    1200 cc/min. N.sub.2                             __________________________________________________________________________     Feed: 99 mole % n-butane                                                       Ex-                           Results, Mole %                                  am-                  Total Hrs.                                                                              C/S   +S/Y  +Y                                   ple Catalyst         on stream                                                                               Bu   Bd   Bu   Bd                                __________________________________________________________________________     35  Houdry C., 1 8" extrusion                                                                       45.0     44.2/77.0 + 11.5/34.1 + 5.1                                           139.0    50.6/80.5 + 12.9/40.7 + 6.5                                           163.0    52.4/80.5 + 12.4/42.2 + 6.5                                           188.0    52.1/80.8 + 12.1/42.1 + 6.3                                           355.0    47.8/83.7 + 11.8/40.0 + 5.7                      36  Houdry C + 0.016 moles                                                                          67.0     43.4/83.8 + 10.4/35.2 + 4.4                          (6.7 wt %) Al.sub.2 (SO.sub.4).sub.3 . 18 H.sub.2 O                                             118.5    38.9/84.4 + 10.1/32.8 + 3.9                                           139.0    38.2/84.6 + 9.8/32.3 + 3.7                       37  Houdry C + 0.037 moles                                                                          47.5     36.7/81.7 + 10.5/30.0 + 3.9                          (14.3 wt %) Al.sub.2 (SO.sub.4).sub.3 . 18 H.sub.2 O                                            96.5     34.7/81.2 + 11.7/28.1 + 4.1                                           171.0    31.4/83.0 + 11.1/26.1 + 3.5                      38  Houdry C + 0.047 moles                                                                          22.0     34.5/80.9 + 9.3/27.9 + 3.2                           (17.6 wt. %) Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O                                            68.5     32.4/81.2 + 11.3/26.3 + 3.7                                           188.5    28.8/81.6 + 11.7/23.5 + 3.4                      39  Harshaw CrC211T, 5/32" dia.                                                                     66.5     45.5/78.7 + 11.1/35.8 + 5.1                          pellets          118.5    52.6/78.4 + 10.09/41.2 + 5.8                                          142.5    52.0/78.2 + 11.1/40.6 + 5.8                                           310.5    51.0/79.6 + 11.7/40.6 + 6.0                      40  Harshaw CrO211 + 0.016 moles                                                                    47.5     33.9/83.7 + 9.2/28.4 + 3.1                           (6.7 wt. %) Al.sub.2 (SO.sub.4).sub.3 . 18 H.sub.2 O                                            96.5     33.1/82.7 + 9.4/27.3 + 3.1                                            171.5    27.9/83.4 + 9.8/23.3 + 2.7                       41  Harshaw Cr0211 + 0.026 moles                                                                    68.5     30.0/82.5 + 9.5/24.7 + 2.9                           (10.7 wt. %) Al.sub.2 (SO.sub.4).sub.3 . 18 H.sub.2 O                                           188.5    28.8/80.2 + 11.8/23.1 + 3.4                      42  Harshaw Cr0211 + 0.037 moles                                                                    18.0     21.9/77.7 + 9.2/17.0 + 2.0                           (14.3 wt %) Al.sub.2 (SO.sub.4).sub.3 . 18 H.sub.2 O                                            143.0    24.1/81.0 + 10.7/19.5 + 2.6                                           166.0    24.2/84.6 + 7.5/20.5 + 1.8                       __________________________________________________________________________

EXAMPLES 43-47

These examples show the use of the catalyst of the invention and a commercial dehydrogenation catalyst in the dehydrogenation of osopentane. The conditions and results are in Table X.

                                      TABLE X                                      __________________________________________________________________________     Conditions: 6" Hg absolute                                                     Feed: 97.6 mole % isopentane                                                                               Percent Selectivities mole % to                                       T.sub. min -  T.sub.max,° F.                                                     Feed to Isoamy-                                                                             Iso-                                                                               Penta-                            Example                                                                             Catalyst  LHSV                                                                               Dehydrogenation                                                                         Coke C.sup.(1)                                                                         lenes                                                                               prene                                                                              dienes                                                                             C.sub.4 's.sup.(2)                                                                 C.sub.3 's.sup.(3)        __________________________________________________________________________     43   MgCr.sub.2 O.sub.4.sup.(4) calcined                                                      1.0 1070-1100                                                                               5.5  52.1                                                                              53.3 24.9                                                                               5.7 4.0 3.2                            to 750° C.                                                         44   Cr0211.sup.(5)                                                                           1.0 1075-1095                                                                               0.6  40.8                                                                              53.1 19.1                                                                               6.6 5.1 5.5                       45   MgCr.sub.2 O.sub.4.sup.(4) calcined                                                      2.4 1000-1040                                                                               1.0  30.3                                                                              69.0 21.3                                                                               3.7 1.7 4.7                            to 750° C.                                                         46   MgCr.sub.2 O.sub.4.sup.(4) calcined                                                      2.4 1070-1130                                                                               2.4  38.4                                                                              61.1 26.8                                                                               4.8 2.6 2.4                            to 750° C.                                                         47   Cr0211.sup.(5)                                                                           2.4 1075-1090                                                                               0.5  26.8                                                                              57.5 15.6                                                                               4.8 5.5 7.4                       __________________________________________________________________________      .sup.(1) Coke free                                                             .sup.(2) All species                                                           .sup.(3) Pentene-1, n-pentane, pentene-2-cis and trans                         .sup. (4) MgCr.sub.2 O.sub.4 + 25 wt. % Al.sub.2 (SO.sub.4) . 16H.sub.2 O      formed into 5/32" pellets                                                      .sup.(5) The Harshaw Chemical Co., Cleveland, Ohio                        

The invention claimed is:
 1. A catalyst composition for use in cyclic dehydrogenation consisting essentially of a chromite compound of the formula MeAl_(x) Cr_(2-x) O₄, wherein Me is Mg or Mg and one or more of the divalent ions of the Ca, Sr, Ba, Fe, Mn, Co, Ni, Cu, Zn, or Cd, said Mg comprising at least 50 atomic percent of said Me ions and x is a number of from more than 0 up to less than 1 and aluminum oxide, the aluminum being present in the catalyst in all forms in an atomic ratio of Al:Cr of 0.04 to 0.8:1.
 2. The catalyst composition according to claim 1 containing more than 50 weight % of said chromite.
 3. The catalyst composition according to claim 2 containing 75 weight % or more chromite.
 4. The catalyst composition according to claim 2 wherein Me is Mg. 